Finishing pigment-resin colored fabrics



Patented Sept. 18, 1945 FINISHING PIGMENT-RESIN COLORED FABRICS Ralph D.Greene, Roy H. Kienle, and Richard D. Vartanian, Bound Brook, N. J.,assignors to American Cyanamld Company, New York, N. Y., a corporationof Maine No Drawing. Application September 2, 1942, Serial No. 457,106

6 Claims.

This invention relates to the permanent finishing of textiles dyed orprinted with pigment-colored compositions.

Printing and dyeing of fabrics by the use of pigment-containingcompositions has achieved an important position in the textile finishingtrades. This is due to the fact that certain colors and effects can beobtained with pigments that are impossible or impractical with truedyes. Unfortunately, however, these pigments themselves must be appliedto the fabric in conjunction with some material which serves as avehicle in applying the pigments and a binder to fix the pigments inplace after they are applied.

One of the earlier proposed procedures was to combine the pigment with alacquer, that is to say a solution of one or more natural resins,synthetic resins, or cellulose esters or cellulose ethers in an organicsolvent in which the pigment was dispersed. In use, this lacquer-pigmentprocess was found to avoid many of the disadvantages of ordinaryprinting with dyes and to enable the production of sharp prints usingsubstantially any desired pigment;

However, the process was not found to be as universally practicable ashad been anticipated. Lacquer-coloring was found to have a serious defect, inherent in the nature of the product, which prevented the processfrom becoming very widely used. The lacquer film which was formed onevaporation of the solventwas so stiff that it bound the textile fiberstogether to produce a colored fabric which was not flexible and had aharsh feel. In addition, the use of lacquer also produced a surfacegloss which in many cases was highly undesirable. It was found thatthese lacquer prints could be improved in pliabilitv if a sufficientamount of plasticizer was used. But this impaired the fastnessproperties without producing any decrease in the continuity in thelacquer film and increasedthe expense of carrying out the process.

In order to overcome the objectionable features associated with the useof lacquers. particularly the stiff hand or harsh feel of the finishedproduct. emulsion-coloring was developed. These emulsions are commonlyof two types. the oilnwater and the water-in-oil types. Each of thesehas certain advantages over the other but both enable the production ofsharp prints and fix d coloring without forming the continuous filmwhich a pears to be responsib e for the undesirable stiffness and glossinherent i lacquer-pigment colored fabrics. As a result. the use ofemulsions, particularly in printing, has to a large extent replacedother types of compositions where the color or effect produced is due tothe use of a pigment.

Unfortunately, however, emulsion prints and dyes, while superior tothose produced from lacquer-type compositions, were also found topossess certain defects which are objectionable from a commercial pointof view. Emulsion-deposited pigments, particularly those from awater-in-oil type emulsion. are quite subject to both wet and drycrocking.

Nor were the fabrics which had been colored by emulsion-depositedpigments as washfast as is desirable in materials to be used for manypurposes. For example, fabrics colored by the use of pigments in thisway, when subjected to standard wash and crock tests were still found tobe inferior as compared with fabrics colored with vat dyes, stabilizedazoic dyes or the like.

In the past, considerable effort has been expended in attempting toovercome these objectionable tendencies of emulsion-deposited pigmentsto crock and wash down. These proposed solutions to the problem havegenerally proceeded 5 along one or the other of two lines. In somecases,

attempts were-made to pro-treat the fabric with a material, such as aresin, which would mechanically or chemically bond the pigment to thefabric. In other cases, attempts were made to include some similarbonding agent in the composition from which the color was deposited.

Many of these procedures were at least partially successful inaccomplishing their intended object in that they did somewhat improvethe wash and crock-fastness whenthey were used. However, theseexpedients were found to have definite limitations. In some cases, theproposed procedures were too expensive for practical purposes. Inothers, the feel or hand of the finished product was impaired so thatthe fabric no longer retained its normal pliability. A compromise wastherefore usually adopted, using only so much of the pigment-fixingagent as would not interfere with the hand, even though this did notgive the desired color-fastness.

Fabrics colored by emulsion-deposited pigments using one of thesemodified compositions or by pro-treating the fabric have fairwash-fastness under some conditions. For example, the best coloredfabrics which can be prepared without impairing their hand according tothese procedures will pass a standard wash test if not preists andColorists Test No. 3, as set forth. in their 1941 Yearbook.

But if these same colored fabrics are first exposed to light, as, forexample, in a standard fadeometer test, and then given the same washtest they wash down badly even though the pigments used are of such anature that the fadeometer test alone does not appreciably alter theshade. Since most fabrics in ordinary use are subject to light as wellas washing these colorings are not entirely commercially satisfactory.

Consequently there still remains a demand for a suitable method ofimproving the wash and crock-fastness of emulsion-deposited pigments.

Obviously the length of exposure to light which may be made withoutproducing fading will vary with the pigment used. With some. of thepoorer pigments fading on exposure to light occurs after only such arelatively short exposure that colorings with these pigments areimpractical regardless of whether or not the color may wash down. 'Thepresent invention is not concerned with such materials but has referenceto the use of-those pigments which are themselves light fast for pcriodsof exposure longer than is required for the action of the light to causethat change in the materials which appears during the subsa uent washtest.

It is, therefore. the object of this invention to provide a novel,simple and effective process whereby textile fabrics which have beendyed or printed with pigment-resin emulsions may be rendered more nearlypermanently washfast and highly resistant to crocking and sloughing. Itis also an object of this invention to accomplish this result withoutproducing a. harsh feel or hand in the fabric analogous to that producedby the older lacquer-printing process.

In general these objects are attained by aftertreating the printed ordyed fabric with an aqueous solution of a water-soluble amidealdehydetype resin which has been etherlfled with a polyhydric alcohol. Thistreatment may be concluded by drying the treated fabric and settingand/or curing the resin to eliminate its watersess excellentwashfastnes's and marked improvement in both wet and dry crockfastnesswithout undergoing any appreciable change in the pliatype resin whichhas been etheriiled with a polyhydric alcohol may be used. The termamidealdehyde" resin as used in the present specification and claims isintended to include aldehyde condensation resins derived from analdehyde biuret, dicyandiamide ormelamine which when etheriiled withapolyhydric alcohol are soluble -resin to bond the pigment and fabric.

assasso alcohol.

It is a still further advantage of the present invention that since itcomprises a protective after-treatment, it requires no specialmodification of the dyeing and printing technique used in coloring thefabric. Nor does it require any modification of the coloringcompositions used in processing the fabric. Thus, the fabric may be dyedor printed using coloring compositions and techniques currentlyavailable. As an illustration of this feature it may be noted that mostdyeing and printing emulsions make use of some These resins must bedeveloped in some way to insure the bond. The after treatment of thepresent invention may be used after printing with the emulsion anddeveloping the resin in the usual way.

It is also a still further advantage of the present invention that theresin need not have been etherified with any particular polyhydricalcohol. Illustrative examples of pclyhydric alcohols which are usefulin preparing the after-treating resin of the present invention includedihydric alcohols such as the glycol, trihydric alcohols such asglycerine and polyhydric alcohols such as pentaerythritol, dipentaerythritol, sorbitol, mannitol containing more than three hydroxygroups.

The effectiveness of the treatment of the present invention ineliminating crocking and washing difficulties encountered with pigmentcolors is even more unexpected when the nature of the pretreating resinsthat have been used in the pre- I vious attempts to solve the problemare considered; For example, amide resins that have been alkylaied withmonohydric alcohols of low molecular weight have been employed both inpretreat- |p ing compositions and as a component of the coloringcomposition without satisfactorily'overcoming the crocking tendency orimproving the .washfastness of pigment-colors.

same materials are used in the after-treating 46 process of the presentinvention they do not prosoluble characteristics. Fabrics so treatedpos-.

duce the desired improvement in color fastness.

Therefore it would appear that the success of the v present invention isdue, in some way which is not wholly understood at the present time, to50 the use of a polyhydric alcohol and the resultant presence of one ormore terminal hydroxy radi- 'and amides such as urea, thiourea,guanidine, co

in aqueous media. However, in some cases, it has been found that certaintypes of-resins when given specific etheriflcation treatments areparticularly useful on specific fabrics. The choice of.

dehyde, the present invention is not necessarilyso limited. Condensationresins made from other aldehydes are also suitable for use. The limitingfactors for all practical purposes is that they cals.

, The invention will be described in greater detail in conjunction withthe following specific 'examples which are meant to be merelyillustrative and do not in any way limit the invention. The parts are byweight unless otherwise noted.

Example 1 blending together 45 parts of iron oxide yellow pigment, 14parts of an oil modified alkyd resin, 7 parts of a 50% solution ofbutylated dimethylol urea in a mixture of xylene and butanol, 24 partsof steam distilled pine oil, 5 parts of oleic acid and 5 parts of 26 B.ammonia on a 3 roller ink mill.

Concurrently, a reducing oil-in-water emulsion was prepared bydissolving 0.4 part of a 4000 centipoise grade of methyl cellulose in81.6 parts of water to which 0.7 part of 26 B. ammonia had been added.To this solution was added a solution consisting of 0.3 parts of oleicacid dissolved in 17 parts of a petroleum distillate fracbewater-soluble and they be adapted to further tion boiling between -250"C. and containing condensation or etheriflcation with a 'polyhydric Whenthese about 16% aromatics, the remainder being predominantly paraiiinicand naphthenic hydrocarbons. By mixing the two solutions whilesubjecting the mixture to high speed stirring a fluid cil-in-wateremulsion was produced.

9 parts of the pigmented resin base was then thoroughly mixed with 91parts of the reducing emulsion. A fabric strip was padded by passing itthrough this mixture and then between rubber squeeze rolls to remove theexcess color, airdrying the treated fabric and heat curing it for 3minutes at 120 C;

A strip of the fabric, colored in this way, was then passed through afinishing solution comprising 8 parts of a 50% aqueous solution of aurea formaldehyde resin etherified with ethylene glycol, 01.5 parts ofwater and 0.5 parts of 85% orthophosphoric acid. The treated strip waspassed between rubber squeeze rolls to remove the excess finishingsolution, dried for 2 hours at 60 C. and heat cured for 3 minutes at 120C.

The untreated dyeing showed a good hand, fair 1 fastness, excellent drycrock resistance and good wet crock resistance.

'washfastness and fair dry and wet crock resist- An intaglio print madefrom the same formulation as that used above in the dyeing operation wasfound to have resultant properties comparable to those described for thedyed fabric.

Emmple' 2 The pigmented resin color base and the reducing oil-in-wateremulsion were prepared as in Example 3 A pigmented resin color base wasprepared by mixing 25.5 parts or a solution of an oil modihand,verygoodwashfastness and fairly good'dry parts of a solution consistingof 48 parts of an oil modified alkyd resin and 32 arts of toluene bymeans of a homogenizing type of stirrer. 2 parts of the finishedemulsion, 15 parts of a petroleum fraction boiling between 135-175 C.with an aromatic hydrocarbon content of about 90%, 15 parts of apetroleum fraction boiling between l60250 C. containing about 16%aromatics, the remainder beingpredominantly parafiinic and naphthenichydrocarbons, are then mixed after which 66 parts of water and 2 partsof glacial acetic acid are stirred lnwith a homogenizing type ofstirrer. A creamy wateri n-oil emulsion resulted.

10 parts of the pigmented resin base was thor oughly mixed with 90 partsof the reducing emule sion and the composition printed on the fabric bymeans of an intaglio printing roll. The print was air dried, and thenheat cured for 3 minuteslat, 120 C. 1 A strip of the printed fabric waspassed through a finishing solution consisting of 5 parts of an 80%aqueous solution of a melamine formaldehyde resin 'etherifled withethylene glycol, 94.5 parts of water and 0.5 parts of 85%orthophosphorie acid. The treated strip was passed be- 4 tween rubbersqueeze rolls to remove the excess finishing solution, dried for 2 hoursat 60 C. "and heat cured for 3 minutes at 120 C. v

The untreated print showed a good hand, good washtastness and poor dryand'wet crockfresisb ance,"whereas the-treated print possessed a goodand wet crock resistance.

Example 1. The procedure of Example 1 was fol- A dyeing made from thesame formulation as that used above min intaglio'printing was found tohave improved crock resistance and washfastness properties scribedforthe print.

trampled -A pigmented resin color base was prepared by deflocculating'50 parts of dichlorobennidine yelcomparable to those low presscakecontainingQOq, solids with 0.4 port had alkyd resin consisting of 15.3parts of the oil modified alkyd in 10.2 parts of a petroleum fractionboiling between 160-250 C. containing about 1 5 5% aromatics, theremainder being. predomiiiantly parafllnic and naphthenic, with 11.5parts of a'solution comprising 3.12 parts of low vis-j cosity ethylcellulose, 6.68 parts of the said petroleumfraction and 1.7 parts ofbutanol. This mixture was blended with 1.8 parts of .tricresylphosphate, 7 parts of copper phthalocyanine pigment and 3.6 parts ofaluminum hydrate and ground on a 3 roller ink mill until a fine anduniform dispersion was obtained. The pigmented material was then blendedtogether with 16 parts of a solution ofa butylated dimethylolurea in amixture of xylene and butanol, 17.3 parts of a petroleum fractionboiling between 135-175" C.

with an aromatic content of abcut 90% and 17.3 parts of a petroleumfraction boiling between A reducing water-in-oil emulsion was-preparedby dissolving 8 parts of sodium lignin sulfonate in 12 parts of waterand emulsifying this in of the sodium salt or disultodinaphthyl methaneand then given one pass through a colloid miil 0.6 part of bentonitewere-stirred into the dispersed color and the mixture was given one passTo this mixture added 2'4 parts of dimethoxymethyl urea, 16' parts Ifthrough a colloid mill.

oi a 25% aqueous solution of trimethylolmelamine, 6 ,parts of the 15eentipoise grade of. methyl cellulose and 4 parts or water. After ringtor 60 minutes the mixture was given onepass through a colloid mill.

A reducing oil-in-water emulsion was to a solutionconsisting of 0.6 partof the trithe remainder being predominantly, parai'nnie and naphthenichydrocarbons were emulsified in.

the solution by means stirrer.v V

10 parts of the pigmented resin base was then thoroughly mixed with 89.5parts of the oil-ins water reducing emulsion followed by the fiddltionof 0.5 partvof orthophosph'oric acid. A fabric strip was padded bypassing it through this mixture and then between rubber squeeze of ahomogenizing im 01' rolls toremove the excess color, air-drying thetreated fabric and heat curing it for 3 minutes at 7 obtained bystirring 6 parts of a 5% aqueous solution of the 4000 centipoise gradeof methyl cellulou in- A strip of the fabric colored in this way wasthen passed through a finishing solution comprising 8 parts of a 50%aqueous solution of a urea formaldehyde resin etherified with ethyleneglycol, 91.5 parts of water and 0.5 part of85% orthophosphoric acid. Thetreated strip was passed between rubber squeeze rolls to remove theexcess finishing solution, dried for 2 hour at 60 c and heat cured for 3minutes at 120 C.

The untreated dyeing showed a fair hand, good washfastness, poor drycrock resistance and very poor wet crock resistance. The treated dyeing,on the other hand, showed a fair hand, excellent washfastness andsurprisingly good dry and wet crockresistance.

An intaglio print made from the same formulation as that used above inthe dyeing operation was found to have resultant properties comparableto those described for the dyed fabric.

It is also another important advantage of the present invention that itcan be readily employed in conjunction with other dyeing and printingoperations in which no pigment coloring is used. For example, oneportion of the fabric surface may be colored with any suitable organicdyestufi such as a vat dye, a stabilized azoic dye or the like or withan ingrain mineral color, the re-,

mainder of the surface may be printed or dyed with an emulsion-depositedpigment and the aftertreatment of the present invention employed. toimprove the color fastness of the pigment colored portion. Similarly anemulsiondeposited pigment may be used to overprint a portion of a fabricsurface which has been previously colored by the use of some organic. orinbeing overlaid by protective coating comprising an urea-formaldehyderesin which resin has been etherified with a polyhydric alcohol. 4

3. A textile fabric, at least a portion of the surface of which iscolored by an emulsiondeposited pigment, said pigment being attached thefibers comprising the fabric by a cured resinous binder selected fromthe group consisting of heat-curable alkyd and heat-curable alkylatedamide-aldehyde type resins, at least the portion colored by said pigmentand said cured binder being overlaid by protective coating comprising amelamine-formaldehyde resin which resin has been etherified with apolyhydric alcohol.

4. In making textile fabrics colored by emulsion-deposited pigments, themethod of improving the wash-fastness, dry crock resistance and wetcrock resistance of the pigmented surfaces which comprises the steps oftreating at least portions of the fabric surface with an emulsioncontaining a light-fast pigment and a binder organic dyestufi and theafter-treament again employed to improve the color fastness of thepigment colored portion.

Where emulsion-deposited pigments have been used to color only a portionof a surface of a fabric, the after-treatment of the present inventionmay be applied either to the whole fabric or to the pigment colored areaonly. The aftertreatment of the present invention produces such a slightchange in' the hand of the fabric that substantially no change isperceptible to the V touch to distinguish the treated areas from thosewhich are not. This may be of particular importance in those cases inwhich the pigmented area comprises only a small portion of the totalsurface and therefore a considerable saving in material can be effectedby after-treating only those portions which are pigment colored.

We claim:

1. A textile fabric, at least a portion of the surface of which iscolored by an emulsion-deposited pigment, said pigment being attachedthe fibers comprising the fabric by a cured resinous binder selectedfrom the group consistin of the heat-curable alkyd and heat-curablealkylated amide-aldehyde type resins, at least the portions colored bysaid pigment and said cured binder being overlaid by protective coatingcomprising an amide-aldehyde resin which resin has selected from thegroup consisting of the heat curable alkyd and heat-curable alkylatedamidealdehyde type resins; curing said binder by heating, whereby thepigment is adhere to the fibers comprising the fabric; treating at leastthe pigmerited portions with an aqueous solution of an uncuredwater-soluble, heat-curable, amide-aldehyde resin, which resinhas beenetherified with a polyhydric alcohol; drying the treated fabric andheating said dri d fabric to cure the heatcurable, amide-aldehyde resin.

5. In making textile fabrics colored by emulsion-deposited pigments, themethod of improving the wash-fastness, dry crock resistance and wetcrock resistance of the pigmented surfaces which comprises the steps oftreating at least portions of the fabric surface with an emulsioncontaining a light-fast pigment and a binder selected from the groupconsistin of the heatcurable alkyd and heat-curablealkylatedamidealdehyde type resins; curing said binder by heating, whereby thepigment is adhered to the fibers comprising the fabric; treating atleast the pigmented portions with an aqueous solution of an uncuredwater-soluble, heat-curable, urea-formaldehyde resin. which resin hasbeen etherifled with a polyhydric alcohol; dryin the treated fabric andheating said dried .fabric to cure the heatcurable, urea-formaldehyderesin.

6. In making textile fabrics colored by emulsion-deposited pigments, themethod of improving the wash-fastness, dry crock resistance and wetcrock resistance of the pigmented surfaces which comprises the steps oftreating at least portions of the fabric surface with an emulsioncontaining a light-fast pigment and a binder selected from the groupconsisting of the heat-curable alkyd and heat-curable alkylatedamidealdehyde type resins: curing said binder by heating, whereby thepigment is adhered to the fibers comprising the fabric: treating atleast the pigmerited portions with an aqueous solution of an uncuredwater-soluble. heat-curable. melamineformaldehyde resin, which resin hasbeen etherified with a polyhydric alcohol: drying the treated fabric andheating said dried fabric to cure the heat-curable.melamine-formaldehyde resin.

RALPH D. GREENE. ROY H. KIENLE. RICHARD D. VARTANIAN.

